The correlation between molecular and atomic Rydberg levels

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Abstract
Calculations have been made on the energies of the Rydberg states of H2O and H2S using a basis of wave functions of the united atoms (Ne or Ar). There is a large mixing of states induced by the potential of the protons, showing that the use of atomic quantum numbers (n, l, m) to designate the Rydberg bands is only a rough guide to their character. The calculated energy levels of H2O are in good agreement with experiment, the only notable failure being in the order of the 1 B 1 and 1 A 1 (3p) levels. The calculations on H2S are intended to be a guide to the interpretation of the spectrum which is so far incomplete. We conclude that the first broad absorption band of H2S (2700–1650 Å) should be made up of at least three electronic transitions, one of which is symmetry forbidden. We also conclude that some of the Rydberg levels are associated with series that extrapolate to the second ionization potential rather than the first.